CN107987407A - A kind of thermoplastic dynamic vulcanized BIIR/PP compositions and preparation method thereof - Google Patents
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The invention discloses a kind of thermoplastic dynamic vulcanized BIIR/PP compositions and preparation method thereof, which is made of the component of following mass parts：BIIR：100 parts；PP：20~30 parts；SEEPS：20~30 parts；Vulcanizing agent：1~3 part；Rubber softening oil：70~90 parts.Its preparation method is as follows：1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, add BIIR and PP is further uniformly mixed, discharged；2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated；3) blend and vulcanizing agent obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel equidirectional two-screw extruder, carries out dynamic vulcanization, extruding pelletization.The thermoplastic dynamic vulcanized BIIR/PP compositions of the present invention have good hermetic seal and a barrier, excellent in mechanical performance, can direct injection molding, production process is simple to operation, and production efficiency height, cost is low, use easy to spread.
Description
Technical field
The present invention relates to a kind of thermoplastic dynamic vulcanized BIIR/PP compositions and preparation method thereof, belong to composite material skill
Art field.
Background technology
Butyl rubber (IIR) is the copolymer by isobutene and isoprene (usually accounting for 1%~5%) preparation, with excellent
Barrier properties for gases it is famous.Brombutyl (BIIR) is formed by butyl rubber bromination, because bromo-reaction occurs on side chain,
Therefore the structure of butyl rubber main chain will not be changed, BIIR has still maintained the good gas barrier of butyl rubber, is medical rubber
The necessary raw material of glue product.The Rubber plug material of conventional sanitation material and pharmaceutical products manufacturing is mainly natural rubber, naturally
Rubber easily reacts, air-tightness is poor, and the public can be pacified by being directly used in medical packaging there are biological safety defect with medicine
Full medication produces very big threat, and state's pencil of national Bureau of Drugs Supervision issue in 2000 notes (2000) No. 462 file regulations：Injection is blue or green
The antibiotic such as mycin sodium salt, potassium salt of penicillin, ampicillin, streptomycin sulphate and infusion preparation, oral liquid biological products, blood
Liquid product will stop using natural rubber plug without exception equal to the end of the year 2004, all be changed to butyl rubber plug, halogenated butyl rubber plug or poly- third
Alkene rubber plug so that natural rubber plug is substituted comprehensively.There is biology to pacify for butyl rubber plug, halogenated butyl rubber plug or polypropylene rubber plug
Entirely, the advantages that chemical stabilization is good, air-tightness is good, easy to clean, is widely used in Key works Drug packing industry.
However, conventional thermosetting medicinal butyl rubber, halogenated butyl rubber product are generally produced using die pressing, it is divided into life
Process, complex technical process, the equipment such as glue is plasticated, compounding agent sieving drying, dispensing, mixing, cut-parts, vulcanization, trimming, washing are thrown
Enter big, production cost height.If a kind of thermoplasticity medicinal rubber material can be developed, thermoset rubber production of articles can be greatly simplified
Technique, production efficiency can also be improved while reducing and polluting.CN 104725732A disclose a kind of medical thermoplastic of soft
Property brombutyl and preparation method thereof, whole preparation process is divided into five steps, complex process, in particular for using mixer
Substep refuels, and efficiency is low, energy consumption is big, and the easy moisture absorption of used phenolic resin vulcanization system, needs that place is dried before use
Reason, the brombutyl of preparation also need that processing is dried before use, and production and service efficiency be not high.
Polypropylene abundance, cheap, easily processed into type, product high comprehensive performance, the bromination with low pole
Butyl rubber has certain compatibility.Styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS) is a kind of
Novel environment-friendly thermoplastic elastomer (TPE), due to the special construction of its strand, can fully absorb rubber softening oil at normal temperatures
And higher elasticity is kept, if by triplicity, thermoplastic BIIR/SEEPS/PP materials are prepared into using dynamic vulcanization technology
Material, it is technically feasible instead of existing thermosetting property IIR and BIIR, and have a vast market prospect.
The content of the invention
It is an object of the invention to provide a kind of thermoplastic dynamic vulcanized BIIR/PP compositions and preparation method thereof.
The technical solution used in the present invention is：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
Brombutyl：100 parts；
Polypropylene：20~30 parts；
Styrene-ethylene-ethylene-propylene-styrene block copolymer：20~30 parts；
Vulcanizing agent：1~3 part；
Rubber softening oil：70~90 parts.
The bromine content of the brombutyl is 1.5wt%~2.5wt%.
The polypropylene be 11~20g/10min of melt index random polypropylene, test condition for 230 DEG C/
2.16kg。
The styrene-ethylene-ethylene-propylene-styrene block copolymer is4033、
4044、4055、4077、At least one of 4099.
The vulcanizing agent is the compound of N, N ' -4,4 '-diphenyl methane dimaleimide (BMI) and zinc oxide.
The N, N ' -4,4 '-diphenyl methane dimaleimide, the mass ratio of zinc oxide are 1：(0.2~1).
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions comprises the following steps：
1) by styrene-ethylene-ethylene-propylene-styrene block copolymer and rubber softening oil in high-speed mixer
It is uniformly mixed, adds brombutyl and polypropylene is further uniformly mixed, discharges；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated；
3) blend and vulcanizing agent obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel in the same direction
Double screw extruder, carries out dynamic vulcanization, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
Each area's temperature of single screw extrusion machine described in step 2) is 100~170 DEG C, and screw speed is 200~300rpm.
The screw speed of double screw extruder described in step 3) is 250~350rpm, and extrusion temperature is 80~185 DEG C.
The screw slenderness ratio of double screw extruder described in step 3) is 48~60.
The beneficial effects of the invention are as follows：The thermoplastic dynamic vulcanized BIIR/PP compositions of the present invention have good hermetic seal
And barrier, excellent in mechanical performance, can direct injection molding, production process is simple to operation, and production efficiency is high, and cost is low, easily
In promoting the use of.
1) present invention can will largely absorb rubber softening oil and keep elastomeric SEEPS to match somebody with somebody with BIIR and PP under room temperature
Close and use, can easily realize granulation on a single-screw extruder without using mixer segmentation oiling mode, substantially increase life
Efficiency is produced, and SEEPS is largely absorbed after rubber softening oil not only has preferable mobility and compared with soft, while also there is superelevation
Resilience, elasticity during BIIR high temperature after vulcanization is higher, and the thermoplastic dynamic vulcanized BIIR/PP compositions of preparation both had
Higher mobility, and there is high low temperature elasticity, meet the requirement of medical rubber stopper；
2) BMI and zinc oxide compounding are used as vulcanizing agent by the present invention, and the fusing point of BMI is 150~160 DEG C, is occurred in BIIR
The scattered crosslinking for triggering BIIR can be fully melted before degraded, and a small amount of addition can reach good vulcanization effect, ZnO exists
It can react at 160 DEG C with BIIR, by removing ZnBr2BIIR conjugated diene structure is occurred, the double bond on BMI with
Diels-Alder reactions occur for the conjugated diene of BIIR, can further promote the crosslinking of BIIR.
Embodiment
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
Brombutyl：100 parts；
Polypropylene：20~30 parts；
Styrene-ethylene-ethylene-propylene-styrene block copolymer：20~30 parts；
Vulcanizing agent：1~3 part；
Rubber softening oil：70~90 parts.
Preferably, the bromine content of the brombutyl is 1.5wt%~2.5wt%.
Preferably, the polypropylene be 11~20g/10min of melt index random polypropylene, test condition 230
℃/2.16kg。
It is further preferred that the melt index that the polypropylene is platform modeling (Ningbo) limited company is 15g/
The random polypropylene of 10min, test condition are 230 DEG C/2.16kg.
Preferably, the styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS) is
4033、4044、4055、4077、At least one of 4099.
Preferably, the vulcanizing agent is N, N ' -4, and 4 '-diphenyl methane dimaleimide (BMI) and zinc oxide are answered
With thing.
Preferably, the N, N ' -4,4 '-diphenyl methane dimaleimide, the mass ratio of zinc oxide are 1：(0.2~
1)。
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions comprises the following steps：
1) by styrene-ethylene-ethylene-propylene-styrene block copolymer and rubber softening oil in high-speed mixer
It is uniformly mixed, adds brombutyl and polypropylene is further uniformly mixed, discharges；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated；
3) blend and vulcanizing agent obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel in the same direction
Double screw extruder, carries out dynamic vulcanization, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
Preferably, each area's temperature of single screw extrusion machine described in step 2) is 100~170 DEG C, screw speed for 200~
300rpm。
Preferably, the screw speed of the double screw extruder described in step 3) is 250~350rpm, extrusion temperature for 80~
185℃。
Preferably, the screw slenderness ratio of the double screw extruder described in step 3) is 48~60.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：20 parts；
SEEPS(4033)：20 parts；
BMI/ZnO：1 part；
Rubber softening oil：70 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 160 DEG C, 170 DEG C, 170 DEG C, screw speed 200rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
48, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
250rpm；Screw zones and head temperature 80,150,160,170,180,185,185,185,185,185,185,185,185/
180℃。
Embodiment 2：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：25 parts；
SEEPS(4033)：20 parts；
BMI/ZnO：1 part；
Rubber softening oil：70 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 160 DEG C, 170 DEG C, 170 DEG C, screw speed 200rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
48, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
250rpm；Screw zones and head temperature 80,150,160,170,180,185,185,185,185,185,185,185,185/
180℃。
Embodiment 3：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 2.0wt%, sinopec Yanshan Petrochemical company)：100 parts；
PP：30 parts；
SEEPS(4033)：20 parts；
BMI/ZnO：1 part；
Rubber softening oil：70 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 170 DEG C, 170 DEG C, 170 DEG C, screw speed 250rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 6 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
300rpm；Screw zones and head temperature 80,150,160,170,175,175,175,175,175,175,175,175,175/
175℃。
Embodiment 4：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 2.0wt%, sinopec Yanshan Petrochemical company)：100 parts；
PP：30 parts；
SEEPS(4033)：20 parts；
BMI/ZnO：2 parts；
Rubber softening oil：80 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 170 DEG C, 170 DEG C, 170 DEG C, screw speed 250rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 6 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
300rpm；Screw zones and head temperature 80,150,160,170,175,175,175,175,175,175,175,175,175/
175℃。
Embodiment 5：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 2.4wt%, Exxon Mobil company)：100 parts；
PP：20 parts；
SEEPS(4055)：20 parts；
BMI/ZnO：3 parts；
Rubber softening oil：70 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 170 DEG C, 170 DEG C, 170 DEG C, screw speed 300rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
350rpm；Screw zones and head temperature 80,150,160,170,175,175,175,175,175,175,175,175,175/
175℃。
Embodiment 6：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：20 parts；
SEEPS(4077)：30 parts；
BMI/ZnO：3 parts；
Rubber softening oil：70 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 170 DEG C, 170 DEG C, 170 DEG C, screw speed 300rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
350rpm；Screw zones and head temperature 80,150,160,170,175,175,175,175,175,175,175,175,175/
175℃。
Embodiment 7：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：20 parts；
SEEPS30 parts；
BMI/ZnO：3 parts；
Rubber softening oil：90 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 170 DEG C, 170 DEG C, 170 DEG C, screw speed 300rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
350rpm；Screw zones and head temperature 80,150,160,170,175,175,175,175,175,175,175,175,175/
175℃。
Embodiment 8：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：30 parts；
SEEPS10 parts；
SEEPS20 parts；
BMI/ZnO：3 parts；
Rubber softening oil：90 parts；
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) SEEPS and rubber softening oil are uniformly mixed in high-speed mixer, then add BIIR and PP and further mix
Discharging after closing uniformly；
2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated, and it is 100 to set each area's temperature of single screw rod
DEG C, 170 DEG C, 170 DEG C, 170 DEG C, screw speed 300rpm；
3) blend and BMI/ZnO obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel same
To double screw extruder, dynamic vulcanization is carried out, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
350rpm；Screw zones and head temperature 80,150,160,170,175,175,175,175,175,175,175,175,175/
175℃.Comparative example 1：
A kind of BIIR/PP compositions, are made of the component of following mass parts：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：130 parts；
PP：30 parts；
BMI/ZnO：3 parts；
Rubber softening oil：90 parts；
The preparation method of above-mentioned BIIR/PP compositions, includes the following steps：
1) BIIR, PP and rubber softening oil are blended in mixer uniformly, not 190 DEG C of mixer temperature, mixing rotor
Rotating speed is 120rpm, mixing time 5min；
2) BMI/ZnO being added into mixer, be uniformly mixed, mixer temperature is 50 DEG C, and mixing rotor rotating speed is 80rpm,
Mixing time is 5min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, it is 20 to set each area's temperature of single screw rod
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 200rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains BIIR/PP compositions；
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
350rpm；Screw zones and head temperature 80,150,160,170,175,175,175,175,175,175,175,175,175/
175℃。
The raw material of embodiment 1~8 and comparative example 1 composition is as shown in the table：
The raw material of 1 embodiment 1~8 of table and comparative example 1 composition table (mass parts)
| BIIR | PP | SEEPS | BMI/ZnO | Rubber softening oil | |
| Embodiment 1 | 100 | 20 | 20 | 1 | 70 |
| Embodiment 2 | 100 | 25 | 20 | 1 | 70 |
| Embodiment 3 | 100 | 30 | 20 | 1 | 70 |
| Embodiment 4 | 100 | 30 | 20 | 2 | 80 |
| Embodiment 5 | 100 | 20 | 20 | 3 | 70 |
| Embodiment 6 | 100 | 20 | 30 | 3 | 70 |
| Embodiment 7 | 100 | 20 | 30 | 3 | 90 |
| Embodiment 8 | 100 | 30 | 30 | 3 | 90 |
| Comparative example 1 | 130 | 30 | 0 | 3 | 90 |
Test case：
The BIIR/PP compositions prepared to embodiment 1~8 and comparative example 1 are tested for the property, test result such as following table institute
Show：
The performance test data of the BIIR/PP compositions of 2 embodiment 1~8 of table and comparative example 1
Testing standard and method：
Shore A hardness：By ASTM-D2240 standard testings；
Tensile strength：By ASTM-D412 standard testings, rate of extension 500mm/min；
Melt index：By ASTM D1238 standard testings, 230 DEG C of test temperature, load 5kg；
Compression set：By ASTM D395B standard testings, test temperature is respectively 23 DEG C and 70 DEG C.
From Tables 1 and 2：
1) due to being not added with SEEPS in comparative example 1, and it with the addition of SEEPS in embodiment 1~8, the heat of embodiment 1~8
The melt index of plasticity dynamic vulcanization BIIR/PP compositions is higher than the BIIR/PP compositions of comparative example 1, and mobility is more preferable,
And the compression set of the thermoplastic dynamic vulcanized BIIR/PP compositions of embodiment 1~8 is less than the BIIR/PP of comparative example 1
Composition；
2) with PP and the increase of rubber softening oil additive amount, thermoplastic dynamic vulcanized BIIR/PP combinations in embodiment 1~8
Increased trend is presented in the tensile strength and melt index of thing.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. thermoplastic dynamic vulcanized BIIR/PP compositions, it is characterised in that：It is made of the component of following mass parts：Brombutyl：100 parts；Polypropylene：20~30 parts；Styrene-ethylene-ethylene-propylene-styrene block copolymer：20~30 parts；Vulcanizing agent：1~3 part；Rubber softening oil：70~90 parts.
- 2. thermoplastic dynamic vulcanized BIIR/PP compositions according to claim 1, it is characterised in that：The bromination fourth The bromine content of base rubber is 1.5wt%~2.5wt%.
- 3. thermoplastic dynamic vulcanized BIIR/PP compositions according to claim 1, it is characterised in that：The polypropylene For the random polypropylene of 11~20g/10min of melt index, test condition is 230 DEG C/2.16kg.
- 4. thermoplastic dynamic vulcanized BIIR/PP compositions according to claim 1, it is characterised in that：The styrene- Ethylene-ethylene-propylene-styrene block copolymer is4033、4044、4055、4077、At least one of 4099.
- 5. thermoplastic dynamic vulcanized BIIR/PP compositions according to claim 1, it is characterised in that：The vulcanizing agent For N, the compound of N ' -4,4 '-diphenyl methane dimaleimide and zinc oxide.
- 6. thermoplastic dynamic vulcanized BIIR/PP compositions according to claim 5, it is characterised in that：The N, N ' -4, 4 '-diphenyl methane dimaleimide, the mass ratio of zinc oxide are 1：(0.2~1).
- 7. the preparation method of the thermoplastic dynamic vulcanized BIIR/PP compositions in claim 1~6 described in any one, it is special Sign is：Comprise the following steps：1) styrene-ethylene-ethylene-propylene-styrene block copolymer and rubber softening oil are mixed in high-speed mixer Uniformly, add brombutyl and polypropylene is further uniformly mixed, discharge；2) blend for obtaining step 1) is transferred to single screw extrusion machine, is granulated；3) blend and vulcanizing agent obtained step 2) is added in high-speed mixer and is uniformly mixed, then is transferred to parallel spiral shells double in the same direction Bar extruder, carries out dynamic vulcanization, extruding pelletization, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
- 8. preparation method according to claim 7, it is characterised in that：Each area's temperature of single screw extrusion machine described in step 2) For 100~170 DEG C, screw speed is 200~300rpm.
- 9. preparation method according to claim 7, it is characterised in that：The screw rod of double screw extruder described in step 3) turns Speed is 250~350rpm, and extrusion temperature is 80~185 DEG C.
- 10. preparation method according to claim 7, it is characterised in that：The screw rod of double screw extruder described in step 3) Draw ratio is 48~60.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791030A (en) * | 2019-12-04 | 2020-02-14 | 北京橡胶工业研究设计院有限公司 | Zinc-free halogenated butyl rubber/polypropylene thermoplastic elastomer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040127643A1 (en) * | 2002-12-26 | 2004-07-01 | Perevosnik Kathleen A. | Thermoplastic elastomers having improved adhesive proterties |
| CN102585319A (en) * | 2012-01-11 | 2012-07-18 | 华东理工大学 | Vulcanizing system of brominated butyl rubber/ polypropylene thermoplastic elastomer sealing material and preparation method for sealing material |
| CN103562302A (en) * | 2011-05-31 | 2014-02-05 | 普立万公司 | Thermoplastic elastomer compounds exhibiting superior compression set properties |
| CN104725732A (en) * | 2014-12-28 | 2015-06-24 | 山东道恩高分子材料股份有限公司 | Low-hardness medical thermoplastic brominated butyl rubber and preparation method thereof |
| CN106280500A (en) * | 2016-08-26 | 2017-01-04 | 广东省石油化工研究院 | A kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition and preparation method thereof |
-
2017
- 2017-11-24 CN CN201711190739.3A patent/CN107987407B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040127643A1 (en) * | 2002-12-26 | 2004-07-01 | Perevosnik Kathleen A. | Thermoplastic elastomers having improved adhesive proterties |
| CN103562302A (en) * | 2011-05-31 | 2014-02-05 | 普立万公司 | Thermoplastic elastomer compounds exhibiting superior compression set properties |
| CN102585319A (en) * | 2012-01-11 | 2012-07-18 | 华东理工大学 | Vulcanizing system of brominated butyl rubber/ polypropylene thermoplastic elastomer sealing material and preparation method for sealing material |
| CN104725732A (en) * | 2014-12-28 | 2015-06-24 | 山东道恩高分子材料股份有限公司 | Low-hardness medical thermoplastic brominated butyl rubber and preparation method thereof |
| CN106280500A (en) * | 2016-08-26 | 2017-01-04 | 广东省石油化工研究院 | A kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王芳等: "硫化剂用量对低硬度动态硫化溴化丁基橡胶/聚丙烯热塑性硫化胶性能的影响", 《合成橡胶工业》 * |
| 罗河胜: "《塑料材料手册（第三版）》", 31 March 2010, 广东科技出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791030A (en) * | 2019-12-04 | 2020-02-14 | 北京橡胶工业研究设计院有限公司 | Zinc-free halogenated butyl rubber/polypropylene thermoplastic elastomer and preparation method thereof |
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